CN110564109B - Preparation method of high-strength solvent-resistant epoxy fiber composite material capable of being rapidly disassembled and recycled - Google Patents
Preparation method of high-strength solvent-resistant epoxy fiber composite material capable of being rapidly disassembled and recycled Download PDFInfo
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- CN110564109B CN110564109B CN201910974152.4A CN201910974152A CN110564109B CN 110564109 B CN110564109 B CN 110564109B CN 201910974152 A CN201910974152 A CN 201910974152A CN 110564109 B CN110564109 B CN 110564109B
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention provides a preparation method of an epoxy fiber composite material with high strength and solvent resistance, which can be rapidly disassembled and recycled, and belongs to the field of high polymer materials. By adopting the epoxy monomer containing exchangeable dynamic bonds and the curing agent as the polymer matrix to be compounded with the fibers, the high-strength solvent-resistant epoxy fiber composite material which is quickly disassembled and can be recycled is obtained. The material has the advantages of excellent mechanical property and high-temperature solvent resistance, and meanwhile, the epoxy fiber composite material can be rapidly disassembled in a specific solvent, so that the cyclic utilization of fibers in the material is realized. The proposal of the invention will further promote the application of the epoxy fiber composite material with high performance, quick detachability and recyclability in practice.
Description
Technical Field
The invention belongs to the field of high polymer materials, and relates to a preparation method of a high-strength solvent-resistant epoxy fiber composite material capable of being rapidly disassembled and recycled.
Background
Due to the advantages of light weight, high strength and the like, the fiber composite material has wide application in the fields of aerospace, automobile industry, rail transit, sports goods and the like. Among many fiber-reinforced polymer composites, epoxy fiber composites occupy a difficult place to replace due to their advantages of stable structure, excellent performance, low shrinkage, chemical resistance, and the like, and include application fields such as automobile parts and wind turbine blades. However, due to the three-dimensional cross-linked network structure of the epoxy, the epoxy composite is difficult to dissolve, reprocess, and recycle after curing, which results in a fiber-reinforced epoxy composite that is difficult to recycle and recycle. With the increase of the yield of the epoxy fiber composite material in the world, a large amount of leftover materials are left in the processing and waste composite materials are generated in decommissioning, and the cyclic utilization of the epoxy fiber composite material is urgently needed from both the aspects of environment and economy. At present, how to realize the quick disassembly and the recycling of the epoxy fiber composite material is still a great problem.
The introduction of reversible dynamic bonds as crosslinking points in the polymer matrix of fiber composites is a new way to achieve the dismantlable and recyclable use of thermoset materials. In the crosslinking network with dynamic bonds, the polymers can be disassembled by utilizing the exchange reaction of the dynamic bonds and small molecules in a solvent, so that the disassembly of the polymer network and the cyclic utilization of fiber materials are realized. However, compared with other physical methods for recycling fiber materials, the method for realizing the disassembly and recycling of the fiber composite material by introducing dynamic bonds into the polymer starts later and is relatively less researched. For example, epoxy fiber composites based on aliphatic dynamic ester bonds have poor strength and require long periods of high temperature heating to be disassembled (Advanced Functional Materials,26(33): 6098-. In addition, the aromatic disulfide bond-based epoxy fiber composite material, which uses an epoxy curing agent having aromatic disulfide bonds, has high strength, but requires a relatively long time for disassembly, and is difficult to achieve rapid disassembly and recycling (Materials Horizons,3(3): 241-. At present, aiming at the epoxy fiber composite material with high strength and solvent resistance, the rapid disassembly and the efficient recycling of the epoxy fiber composite material are still difficult to realize. Therefore, the preparation method of the epoxy fiber composite material with high strength, solvent resistance, quick detachability and recyclability further promotes the application of the composite material with high performance, quick detachability and recyclability in practice.
Disclosure of Invention
The invention provides a preparation method of an epoxy fiber composite material with high strength, solvent resistance, quick detachability and recycling. The epoxy fiber composite material which is high in strength, solvent-resistant, fast detachable and recyclable is prepared by respectively adopting an epoxy monomer with exchangeable dynamic bonds and an epoxy curing agent with exchangeable dynamic bonds to be compounded with a fiber material and then carrying out curing reaction at high temperature.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an epoxy fiber composite material with high strength, solvent resistance, quick detachability and recycling comprises the following steps; the epoxy fiber composite material is prepared by taking an epoxy monomer with exchangeable dynamic bonds and an epoxy curing agent with exchangeable dynamic bonds as polymer matrixes, compounding the polymer matrixes with fiber materials, and then carrying out curing reaction at high temperature to obtain the epoxy fiber composite material which is high in strength, solvent-resistant, fast detachable and recyclable.
In one embodiment, the exchangeable dynamic bonds include any of dynamic covalent bonds and dynamic non-covalent bonds capable of undergoing an exchangeable reaction, such as carboxylic ester bonds, vinyl urethane bonds, phenylboronic ester bonds, siloxane bonds, disulfide bonds, aromatic disulfide bonds, exchangeable alkyl and olefin bonds, and the like.
In one embodiment, the fibers include any fiber material that can be combined with epoxy resin, such as long carbon fibers, short carbon fibers, carbon fiber cloth, long glass fibers, short glass fibers, and glass fiber cloth.
In one embodiment, the specific solvent includes dithiothreitol or dithiothreitol, 1, 3-propanedithiol, ethylene glycol, glycerol, and the like, which are capable of undergoing an exchange reaction with the exchangeable dynamic bond.
Compared with the prior art, the invention has the beneficial effects that:
compared with the common epoxy fiber composite material, the epoxy fiber composite material has high strength and solvent resistance due to the exchangeable dynamic bonds in the epoxy monomer and the curing agent, and can be quickly disassembled in a certain solvent and recycled through the quick exchange reaction of the exchangeable dynamic bonds and small molecules in the solvent. The invention provides a new way for the rapid disassembly and recycling of the high-performance solvent-resistant epoxy fiber composite material.
The epoxy monomer with exchangeable dynamic bonds and the epoxy curing agent with exchangeable dynamic bonds are selected to be compounded with the fiber material, when the epoxy fiber composite material and the micromolecules in a specific solvent are subjected to exchange reaction, the polymer is disassembled into the micromolecules and is more easily dissolved in the specific solvent, so that the disassembling speed of the epoxy fiber composite material is greatly accelerated, the time required by disassembling is shortened, and the epoxy fiber composite material is quickly disassembled and efficiently recycled.
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FIG. 1 shows the design, preparation, rapid disassembly and recycling of the epoxy carbon fiber composite material.
FIG. 2 shows solvent resistance of epoxy carbon fiber composite material and mechanical properties before and after recycling.
Detailed Description
The present invention will be further described with reference to the following examples, which are intended to illustrate only some, but not all, of the embodiments of the present invention. Based on the embodiments of the present invention, other embodiments used by those skilled in the art without any creative effort belong to the protection scope of the present invention.
Example 1:
epoxy monomer (BGPDS) with aromatic disulfide bond and epoxy curing Agent (AFD) with aromatic disulfide bond are compounded with carbon fiber material, and curing is carried out for 3 hours at the temperature of more than 160 ℃ to obtain the epoxy carbon fiber composite material which is high in strength, solvent-resistant and fast in disassembly and based on the aromatic disulfide bond. The preparation method specifically comprises the following steps of adopting dithio-diphenyl-diglycidyl ether as an epoxy monomer, dithio-diphenylamine as an epoxy curing agent, three-dimensional carbon fiber cloth as a fiber material, fully soaking the polymer and the fiber material, and reacting at 160 ℃ for 3 hours to prepare the aromatic disulfide bond-based epoxy carbon fiber composite material. Subsequently, the rapid disassembly and fiber recovery of the epoxy composite was achieved by soaking with a dilute solution of Dithiothreitol (DTT) at room temperature or with heating, as shown in FIG. 1. After the epoxy matrix is quickly and completely dissolved in the solvent through the exchange reaction with dithiothreitol, the residual carbon fiber material is recovered and compounded with the epoxy monomer and the epoxy curing agent, so that the cyclic utilization of the carbon fiber material is realized. As shown in FIG. 2, the epoxy carbon fiber composite material has excellent high-temperature solvent resistance, and the mechanical properties of the epoxy carbon fiber composite material can be still maintained at the initial level before and after recycling.
Example 2:
the epoxy monomer with the aromatic disulfide bond and the epoxy curing agent with the aromatic disulfide bond are compounded with the glass fiber material and cured for 3 hours at the temperature of more than 160 ℃ to obtain the high-strength solvent-resistant rapidly-decomposable epoxy glass fiber composite material based on the aromatic disulfide bond. The preparation method specifically comprises the following steps of adopting dithio-diphenyl-diglycidyl ether as an epoxy monomer, dithio-diphenylamine as an epoxy curing agent, three-dimensional glass fiber cloth as a fiber material, fully soaking the polymer and the fiber material, and reacting at 160 ℃ for 3 hours to prepare the aromatic disulfide bond-based epoxy glass fiber composite material. Subsequently, the rapid disassembly of the epoxy composite and the recovery of the fibers are achieved by soaking with a dilute solution of dithiothreitol at room temperature or with heating. When the epoxy matrix is quickly and completely dissolved in the solvent through the exchange reaction with dithiothreitol, the residual glass fiber material is recovered and compounded with the epoxy monomer and the epoxy curing agent, so that the cyclic utilization of the glass fiber material is realized.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (2)
1. A method for quickly disassembling and recycling a high-strength solvent-resistant epoxy fiber composite material is characterized by comprising the following steps; taking an epoxy monomer with exchangeable dynamic bonds and an epoxy curing agent with exchangeable dynamic bonds as a polymer matrix, fully soaking and compounding the polymer matrix and a fiber material, then carrying out curing reaction at high temperature to obtain a high-strength solvent-resistant epoxy fiber composite material which can be rapidly disassembled and recycled, meanwhile, the epoxy fiber composite material can be rapidly disassembled under a specific solvent, the residual fiber material is separated, cleaned and recycled, and is compounded with the epoxy monomer and the epoxy curing agent again to obtain a fiber reinforced composite material, and the mechanical property of the fiber reinforced composite material is kept equivalent to the initial level after recycling, so that the recycling of fibers in the material is realized;
the epoxy monomers capable of exchanging dynamic bonds are: dithio-diphenyl-diglycidyl ether;
the epoxy curing agent capable of exchanging dynamic bonds is as follows: dithio diphenylamine;
the specific solvent comprises dithiothreitol.
2. The method of claim 1, wherein the fibers comprise long carbon fibers, short carbon fibers, carbon fiber cloth, long glass fibers, short glass fibers, and glass fiber cloth.
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| CN113150500B (en) * | 2021-04-30 | 2022-07-26 | 中国工程物理研究院化工材料研究所 | Winding-formed fiber-reinforced epoxy glass polymer composite material |
| CN114891320B (en) * | 2022-05-07 | 2023-09-19 | 重庆国际复合材料股份有限公司 | Epoxy resin/chopped glass fiber composite material and preparation method thereof |
| CN114989563B (en) * | 2022-06-01 | 2023-09-19 | 西南科技大学 | Method for regulating and controlling aromatic disulfide epoxy electrochromic wave band |
| CN115594949A (en) * | 2022-10-10 | 2023-01-13 | 重庆国际复合材料股份有限公司（Cn） | Recyclable epoxy wind turbine blade material and preparation method and recycling method thereof |
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| JP2015209509A (en) * | 2014-04-28 | 2015-11-24 | 京セラケミカル株式会社 | Epoxy resin composition and resin-sealed electronic component device |
| CN106947054A (en) * | 2017-03-27 | 2017-07-14 | 中国工程物理研究院化工材料研究所 | In a mild condition can rapid disassembling thermosets preparation and disassembling method |
| CN109762139A (en) * | 2019-01-22 | 2019-05-17 | 中国工程物理研究院化工材料研究所 | It can weld the preparation method that can repair and can reprocess molding thermosetting polymer under a kind of moderate temperature |
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| JP2015209509A (en) * | 2014-04-28 | 2015-11-24 | 京セラケミカル株式会社 | Epoxy resin composition and resin-sealed electronic component device |
| CN106947054A (en) * | 2017-03-27 | 2017-07-14 | 中国工程物理研究院化工材料研究所 | In a mild condition can rapid disassembling thermosets preparation and disassembling method |
| CN109762139A (en) * | 2019-01-22 | 2019-05-17 | 中国工程物理研究院化工材料研究所 | It can weld the preparation method that can repair and can reprocess molding thermosetting polymer under a kind of moderate temperature |
Non-Patent Citations (3)
| Title |
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| Degradable epoxy resins prepared from diepoxide monomer with dynamic covalent disulfide linkage;Takahashi A, et al;《Polymer》;20151201;第82卷;319-326 * |
| Preparation of self-healing, recyclable epoxy resins and low-electrical resistance composites based on double-disulfide bond exchange;Zhou F, et al;《Composites Science and Technology》;20180729;第167卷;79-85 * |
| Takahashi A, et al.Degradable epoxy resins prepared from diepoxide monomer with dynamic covalent disulfide linkage.《Polymer》.2015,第82卷第319-326页. * |
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